Manufacture of sulphur containing dyes and product



Patented June 9, 1931 UN TED STATES P ENT Prior. 7

OSKAR sPENGLER, or BERL N-NE B BELSBERG, AND wnftNER irtTL nR, or L IPzm.

GERMANY, ASSIGNORS TO GENERAL ANI INE worms-1N0, on NEW YORK, N. Y.

MANUFACTURE OF SULPHUR CONTAINING DYns AND 3930131101 U I Ho Drawing. Application filed April 3'0, 1927,8eria1N0. 188,039, and in Germany February 20, 1925.

The present invention relates to new s'ul phur-containing dyestuffs and to a process of preparing them.

The parent organic substance is treated 5 with a sulphocyanogen or an agent yieldingsulphocyanogen and the sulphocyanogen compound thus produced is-convertedinto the dye by a'treatinent' with an alkali. As.

parent materials are particularly suitable aminoand hydroxyaryl compounds'and the various derivativesof such compounds which are adapted to be transformed intodyestuff-s and in some cases are already dyestuifs.

Simple aromatic amines, such as aminobenzene, and hydroxy compounds, such as hydroxybenz'ene and hydroxynaphthalene,

have been shown to be capable of substitution by means of sulphocyanogen, (Sederback,

Annalen der Chemie, .419, page 217 Kaufmann, Bend. pharmaz. Gesellschaft 33,144). if

It could not be foreseen, however, from the existing state of knowledge that even several sulphocyanogen groups can be introduced with similar'ease into complicated d'yestu'lf: components or even dyestuffs of high molecu 1 lar weight-which contain amino-groups or hydroXy-groups or both of these.

Thes'ulphocyanogen compounds serving as intermediate products may advantageously be madeby the process described in U..S. Letters Patent No.1,594,697 and No. 1,687 ,1-

596 by causing solutions obtainable by double decomposition between a halideoffjsulphuric acid and a sulphocyanate to react on an 5 aminoor hydroXyaryl-compound. A By boiling the compoundcontainin-g" sulpho-cyanogen with alkali or alkalifsulphide thereisobtained, particularly if'severa l sul- 40 phocyanogen groups arepresent in the molecule, apure dyestuif soluble in alkali sulphide.

If the sulphocyanogen. compound is changed by boiling it with alkali sulphide thereijis substance; this is filtered and. gradually disulphide, whereby a deep; bluesolution is I compoundof the dyestuif or the dyestuff I The following examples illustrate the in 1 i vention, the parts being by weight-1+ Example 1.To a suspension 'o'f 2.5-parts of 8-hydroxy-L2-naphthophenazine of the probable formula in 305O parts of' -carbon tetra chloride is parts of sulphuryl'chloridewith 12 parts of lead sulphocyanateiin parts of carbon tetrachloride. Almost immediately thev azine 1s changed to a dark, nearly, insoluble resinous solidifies to a brown crystalline powder.

4 parts of this azine containing sulphocyanogen are introduced gradually. into parts of a boiling aqueous solution of sodium produced. After this has been boiled for a short time it is diluted with about 250 parts: of boiling water and'then filte'red When the filtrate has cooled to" about 50C. the leuco compound of the sulphur-containing lyestufiis precipitated in the form-of yel- P i l I Orange l y c ut ous. addition of" obtained a solution from, which, by acid ficav44'; tionor by passing a current of air, the leuco acetic acid. F iber; dyed in, a sodium sulorange yellow when the leuco-compound is oxidized on the fiber; this dyeing is char acterized by its excellent fastness, particularlyto chlorine.

. Example 2. 1%) a suspension of 3 parts of 8.8 -dihydroxy-12.1.2-dinaphthazine of the probable formula:

of the azine are introduced gradually into 80 parts of a boiling aqueous solution of sodium disulphide of 50 per cent. strength. After boiling for about half-an-hour the deep blue solution is diluted with about 900 parts of'boiling water and then filtered and the product is worked up as described in Example 1. The red brown dyestutf thus obtained yields a clear red of excellent fastness when oxidized on the fiber.

Emample 3.To a suspension of 5 parts of tri-diphenylaminemethanehydrochloride of e; the probable formula:

O I 0/ j Y D -O in 100 parts of chloroform is added a solution made by the reaction of 8.1 parts of sulphuryl chloride with 30 parts of lead sulphocyanate in 50'parts of chloroform. The parent material very quickly dissolves to a deep blue solution. After coolingwith ice- Water and vi orously shaking the solution, there crystallizes ina short time the sulphoc anogen product which after 20 minutes is filtered; it is a copper red crystalline powder of bronze lustre. f

8 parts of this dyestufi containing sulphocyanogen are dissolved in boiling alcohol when there are added 50'parts of an aqueous solution of sodium sulphideof 50 per cent.

strength. whereupon the solution becomes violet red. When ithas been boiled for some hours it isfiltered hot and after addition of 100 parts of Water the alcohol is distilled.

From the nearly colorless aqueous solution acetic acid precipitates the leuco-compound of the sulhur-containing dyestui'l in the form of nearly colorless flocks. Cotton is dyed by the dyestufi' clear blue tints.

Ewample 4.To a suspension of 3.5 parts of tolusa'franine of the probable formula:

in 100 parts of carbon-tetrachloride there is added a solution made by reaction of 5.4 parts of sulphuryl chloride with 16 parts of lead sulphocyanate in parts of carbon tetrachloride. There is immediately produced a dark, insoluble resinous product of reaction which, after filtration soon becomes a black crystalline powder of feeble bronze lustre.

7 parts of this compound containingsulphocyanogen are dissolved in 50 parts of a boiling aqueous solution of sodium disulphide of 50 per cent. strength. The solution is gradually mixed with 400 parts of boiling water and after filtration is worked up as described in Example 1. The leuco-compound oxidizes on the fiber to a reddish violet.

Having now particularly described and acertained the nature of our said invention and in what manner the same is to be performed, we declare that what we claim is 1. A process of making sulphuncontaining 105 dyestuffs which comprises treating an aromatic compound containing at least one of the groups, NH and OH, with a solution containing the reaction product of a sulphurylhalide and a sulphocyanate and treating the sulphocyanogen compound thus produced with an alkaline substance at a temperature not exceeding essentially 100 C.

2. A process of making sulphur-containing dyestufi's which comprises treating an aromatic compound containing'at least one of the groups, NH and -OI-I, with a compound yielding sulphocyanogen and treating the sulphocyanogen compound thus produced with an alkaline substance at a temperature not exceeding essentially 100 C.

3. A process of making sulphur-containing dyestufis which comprises treating an aromatic compound containing-at least one of the groups, NH and OH, with a solution 5 containing the reaction product of a sulphurylhalide and a sulphocyanate and boiling the sulphocyanogeneompound thus produced with an alkalimetal sulphide at a temperature not exceeding essentially 100 C.

4. Aprocess o f making sulphur-containing sulphide, said dyestuffs being a red-brown dyestuffs which comprises treating an arosubstance dyeing fiber from a sodium S1111 matic azine containing at least one of phide vat a clear red shade of excellent fastthe groups, NH and OH, with a soluness.

tion containing the reaction product of a s'ulphurylhalide and a sulphocyanate and tures.

boiling the sulphocyanogen compoundfthus produced with an alkali metal sulphide.

5. A process of making sulphur-containing dyestufl's which comprises treating an arcmatic azine containing at least one OH group, with a solution contaiining the reac-' tion product of a sulphurylhalide and a sulphocyanate andboiling the sulphocyanogen compound thus produced with an alkali metal sulphide. 1

6. A process of making sulphur-containing In testimony whereof we affix our signa- OSKAR SPENGLER.

WERNER MULLER. Y

dyestuffs which comprises treating 8.8'-dihydroxy-1.2.1.2-dinaphthaZinewith a solution containing the reaction product of a sul phurylhalide and a sulphocyanate and boiling the sulphocyanogen compound thus produced with an alkali metal sulphide.

7. As new products, the sulphur-contain- 7 ing dyestuffs which may be produced by treating an aromatic compound contaming at least one of the groups, NI-I and OH,

with a solution containing thereacti'on prodv1 1 not of a sulphurylhalide and a sulphocyanate I and treating the sulphocyanogen compound thus produced with an alkaline substance at a temperature not exceeding essentially 100 C.

8.v As new products, the sulphur-containing dyestuffs which may be produced by treatsolution containing the reaction product of a sulphurylhalide and a sulphocyanate and boiling the sulphocyanogen compound thus 9. As new" products, the sulphur-containv I ing dyestufis which may be produced by tr-eating an aromatic azine containing at 1 least one of the groups, NH and OH,

' with a solution containing the reaction prodnot of a sulphurylhalide and a sulphocyanate and boiling the sulphocyanogen compound thus produced with an alkali metal sulphide. i

10. As new products, the sulphur-contain ing dyestufi's which may be produced-by treating an aromatic azine containing at least one OH group, with a solution containing the reaction product of a sulphurylhalide and a sulphocyanate and boiling the sulphocyanogen compound thus produced with an alkali metals sulphide.

11. As a new product, a sulphur-containing dyestuffs which maybe 'producedby treating 8.8-dih'ydroxy-l.2.1'.2-dinaphthazine with a solution containing the reaction product of a sulphurylhalide and a sulphocyanate and boiling the sulphocyanogen compound thus produced with an" alkali metal ing an aromatic compound containing at least. i one of the groups, 'NH and -OH, with a 

